CN101524583A - Method for degrading perfluorinated compounds - Google Patents

Method for degrading perfluorinated compounds Download PDF

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Publication number
CN101524583A
CN101524583A CN200910081468A CN200910081468A CN101524583A CN 101524583 A CN101524583 A CN 101524583A CN 200910081468 A CN200910081468 A CN 200910081468A CN 200910081468 A CN200910081468 A CN 200910081468A CN 101524583 A CN101524583 A CN 101524583A
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substituted compounds
fluorine substituted
pfoa
compounds
reducing substances
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张彭义
赵宝秀
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Tsinghua University
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Tsinghua University
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Abstract

The invention discloses a method for degrading perfluorinated compounds, comprising the following steps: under the oxygen-free condition, belta-Ga2O3 is adopted as a photocatalyst. Ultraviolet with the wavelength of 185-254nm is used for irradiating the perfluorinated compounds to be degraded. The method for degrading the perfluorinated compounds has the advantages that: the technique has a simple structure and can be implemented under normal temperature and normal pressure without complex equipment; the initial concentration of the perfluorinated compounds is not required, and the perfluorinated compounds with any concentration and any pH value can be processed by the method of the invention; the toxicity of degraded products is lowered, and the products can be further processed by other methods.

Description

A kind of method for degrading perfluorinated compounds
Technical field
The present invention relates to a kind of method for degrading perfluorinated compounds.
Background technology
(Perfluorinated Compounds PFCs) is meant the compound that the hydrogen (H) that links to each other with carbon atom (C) in the organic constitution is all replaced by fluorine (F) to fluorine substituted compounds.Because the electronegativity of fluorine is very big, so the structure of this compounds and stable is difficult to be degraded.Particularly with perfluoro caprylic acid (Perfluorooctanoic acid, PFOA, C 7F 15COOH) and perfluoro octyl sulfonic acid salt (Perfluorooctane sulfonate, PFOS, C 8F 17SO 3 -) be that the fluorine substituted compounds of representative, traditional treatment technology are difficult to it is decomposed.
Fluorine substituted compounds was brought into use from the 1950's, was widely used in industry and consumer goods industry, comprised the protective finish, paper coating, insecticide component, fire retardant, surfactant of fabric and carpet etc.A large amount of both at home and abroad investigation find that fluorine substituted compounds has following characteristic: (1) persistence: conventional method is difficult to degraded, can both stable existence in aerobic or oxygen-free environment, and wherein, PFOS is under 25 ℃ temperature conditions, and the half-life was above 41 years; (2) bioaccumulation: have two characteristics of hating, absorbed by organism, finally be enriched in blood, liver, kidney or the brain of organism in the mode of breathing and food chain; (3) toxicity: have multiple toxicity such as genetoxic, arrenotoky toxicity, neurotoxicity, development toxicity and endocrine interference effect, be considered to the environmental contaminants that a class has many devices of whole body dysentery; (4) ability of remote migration: ability with long distance environment transmission, pollution range is very extensive, investigated underground water, surface water and seawater in the worldwide, even connect in unfrequented Arctic, ecological environment sample, wild animal and the human body without exception the trace that exists fluorine substituted compounds to pollute.
After recognizing the harm of fluorine substituted compounds, many countries and international organization successively propose corresponding emergency measure.The maximum 3M companies of chemical industry manufacturer in the whole world in 2000 at first propose to gradually reduce production and the use of PFCs; Calendar year 2001, the U.S. listed PFOS in the environmental contaminants blacklist of State Bureau of Environmental Protection's emphasis monitoring; The 34th the chemicals committee joint conference that international economy in 2002 and development and cooperation organize OECD to hold is defined as PFOS " material that is present in environment lastingly, has biological savings property and the mankind are harmful to "; European Parliament in 2006 and council of ministers unite the issue " instruction (2006/122/EC) of selling and using about the restriction PFOS; The 4th conference of contracting party to holding in May, 2009 recommended five kinds of alternative materials of new POPs in " Convention of Stockholm " POPs examination board in 2007 third session, wherein just comprise PFOS and fluoride thereof (PFOSF), so the use of PFOS and derivative thereof will be closed down comprehensively.
Though recognized the harm of PFOA and PFOS in the world, and formulated corresponding restriction regulations, the problem of how to degrade safely and efficiently PFOA and PFOS is not also solved preferably.Method for degrading perfluorinated compounds mainly contains phonochemistry method, photochemical method, thermochemical method and absorption method at present.The PFCs though absorption method can effectively be degraded is that main subsequent treatment means are dangerous with burning method, deals with improperly to cause secondary pollution; Thermochemical method is owing to needing the above high temperature of 1000C, to having relatively high expectations of equipment; Phonochemistry method also can effectively degrade PFOS and PFOA, but reaction condition is harsh, and concentration how to control the interface bubble is key factor; In the photochemical method, the vacuum-ultraviolet light of the 185nm PFOA that can degrade effectively, the ultraviolet light of 254nm does not then almost have degradation.
Photochemical method is widely used for degradation of organic substances because of its special superior function, PFOA and PFOS but the common photocatalysis oxidation method based on titanium dioxide optical catalyst that adopts can not be degraded effectively, its reason is, this method mainly relies on hydroxyl radical free radical to come degradation of organic substances, and hydroxyl radical free radical can not replace the fluorine in the perfluorochemical or add in the perfluorochemical and cause the decomposition of perfluorochemical.
Summary of the invention
Pollute in order to tackle fluorine substituted compounds (PFCs), the invention provides a kind of method for degrading perfluorinated compounds.
Method for degrading perfluorinated compounds provided by the present invention may further comprise the steps: under oxygen free condition, adopt β-Ga 2O 3As photochemical catalyst, be the UV-irradiation fluorine substituted compounds of 185-254nm with wavelength, make the fluorine substituted compounds degraded.
In the said method, described fluorine substituted compounds is perfluoro caprylic acid or perfluoro octyl sulfonic acid salt.
In the said method, described oxygen free condition is by feeding inert gas or reducibility gas realization in reaction system.
In the said method, described ultraviolet light wavelength specifically can be 254nm.
In the said method, described fluorine substituted compounds and β-Ga 2O 3Mol ratio be 1: (15-40), specifically can be 1: 37.
In order to accelerate the degradation speed of fluorine substituted compounds, can in reaction system, add reducing substances, to remove hydroxyl radical free radical; Described reducing substances is solubility salt compounded of iodine, solubility thiosulfate or organic matter, specifically can be KI, sodium thiosulfate, methyl alcohol or phenol.
In the said method, the mol ratio of described fluorine substituted compounds and described reducing substances is 1: (0-15), specifically can be 1: 0.7.
The principle of degrading perfluorinated compounds of the present invention is: in the oxygen-free environment, and under UV-irradiation, catalyst β-Ga 2O 3The light induced electron that produces that is stimulated is attacked PFOA (C 7F 15-COOH) or PFOS (C 8F 17-SO3 -) C-C and the C-S skeleton that link to each other with carboxyl or sulfonic group in the molecule, form C 7F 15Or C 8F 17Group; Through hydrolysis and take off HF reaction, form C again 6F 13COOH and fluorine ion (F -); The new short chain perfluor substituted carboxylic acid C that forms 6F 13Few CF is decomposed in the attack that COOH is subjected to light induced electron equally again 2The perfluor substituted carboxylic acid C of group 5F 11COOH; This process is carried out continuously, and final PFOA and PFOS all are broken down into CO 2And fluorine ion.
Adopt Ultra Performance Liquid Chromatography-tandem mass spectrometer (UPLC-MS/MS) that the intermediate product that above-mentioned course of reaction generates is analyzed, the result shows, the main intermediate product that generates is the perfluorocarboxylic acid compound (PFCAs) of short chain, and ion chromatography also detects the fluorine substituted compounds decomposition and produced fluorine ion.
Above-mentioned course of reaction will be carried out under the condition of anaerobic, if oxygen exists, oxygen can combined catalyst β-Ga 2O 3The light induced electron on surface generates H 2O 2, H 2O 2Under ultraviolet excitation, can form hydroxyl radical free radical, thereby reduce the concentration of light induced electron, weaken the efficient of photo catalytic reduction.Because fluorine atom is the strongest atom of occurring in nature oxidisability, there be not oxidisability (the taking Electronic Performance by force) group stronger than fluorine, so can not replace fluorine on the fluorine substituted compounds, so under the strong oxidizing property condition, can not realize the defluorinating and degrading complete of fluorine substituted compounds with the group of a strong oxidizing property such as hydroxyl radical free radical (OH).
Because PFOA and PFOS are degraded by the photo catalytic reduction approach, in order to improve the efficient of photo catalytic reduction, can in above-mentioned course of reaction, add the reducing substances that to remove hydroxyl radical free radical, as KI, sodium thiosulfate or methyl alcohol etc., to suppress the compound of light induced electron-hole, improve the photon utilization rate.
The present invention is with the semi-conducting material β-Ga of the high conduction band of broad-band gap 2O 3As photochemical catalyst, in oxygen-free environment, under UV-irradiation, the electronics that utilizes optical excitation to produce comes the deoxidization, degradation fluorine substituted compounds.Method for degrading perfluorinated compounds of the present invention has the following advantages: process structure is simple, carries out under normal temperature and pressure conditions, does not need complex apparatus; Initial concentration to fluorine substituted compounds does not require, and the fluorine substituted compounds under concentration and the pH value condition all can adopt the inventive method to handle arbitrarily; The toxicity of catabolite reduces, and is easy to adopt additive method further to handle.
Method for degrading perfluorinated compounds of the present invention can be used for eliminating the fluorine substituted compounds of water, air or soil.
Description of drawings
Fig. 1 is the reaction unit figure of photocatalytic degradation fluorine substituted compounds
Fig. 2 is the photocatalytic degradation of perfluoro caprylic acid (PFOA)
Fig. 3 is the photocatalytic degradation of perfluoro octyl sulfonic acid salt (PFOS)
Fig. 4 adds the influence of reducing substances to photocatalytic degradation PFOA
Fig. 5 is the photocatalysis defluorinate of PFOA
Fig. 6 is the change in concentration of the intermediate product of photocatalytic degradation PFOA
The specific embodiment
Experimental technique described in the following embodiment if no special instructions, is conventional method; Described reagent and biomaterial if no special instructions, all can obtain from commercial channels.
The photocatalytic degradation of embodiment 1, perfluoro caprylic acid (PFOA)
The reaction unit of photocatalytic degradation fluorine substituted compounds as shown in Figure 1.This device comprises following parts: light source 1 is used for the ultraviolet light of emission wavelength less than 400nm; Quartz socket tube 2 can see through ultraviolet ray, is used to isolate ultraviolet ray and reaction solution; Reaction vessel 3 is places of fluorine substituted compounds degraded; Aeration board 4 is used for reducibility gas such as inertia such as nitrogen, argon gas or ammonia are fed reaction vessel 3, to drive the oxygen in the reaction vessel 3 away, can also play the effect of stirring reaction solution simultaneously; Gas adds inlet 5, is used for adding inert gas or reducibility gas to reaction system; Condensed water imports and exports 6; Cooling water circulating device 7 is used for the circulation of cooling water, reduces the heat because of uviol lamp produced; Sample tap 8 is used for timing sampling.
To 100mL 7.25 * 10 -5Add β-Ga in the PFOA aqueous solution of mol/L 2O 3Powder stirs 3h, the homogeneous phase solution that obtains clarifying, β-Ga in the homogeneous phase solution 2O 3Final concentration be 2.67 * 10 -3Mol/L.
As shown in Figure 1, open the aeration board 4 of reaction unit bottom, nitrogen, oxygen and air are added inlet 5 from gas respectively to be passed into the reaction vessel 3, homogeneous phase solution with the above-mentioned clarification that obtains joins in the reactor 3 again, aeration is about half an hour, open cooling water circulating device 7 and light source 1 then, begin reaction.Extract reaction solution from sample tap 8 at regular intervals, detect PFOA and short chain perfluorocarboxylic acid compound concentrations thereof, adopt electron spray anion (ESI) pattern among the UPLC-MS/MS to measure PFOA and short chain perfluorocarboxylic acid compound concentrations thereof.
β-Ga 2O 3The effect of photocatalytic degradation PFOA as shown in Figure 2.The result shows that different aeration atmosphere (oxygen, air or nitrogen) are different to the photocatalytic degradation effect of PFOA.Wherein, the oxygen atmosphere is to not effect of degraded PFOA, and this is because oxygen and light induced electron react, thereby has weakened the efficient of photocatalytic degradation PFOA, and this has proved that also PFOA is not that approach by photochemical catalytic oxidation is degraded; And nitrogen atmosphere can promote the degraded of PFOA greatly, and this is because nitrogen can be driven the oxygen in the reaction system effectively, improves photo catalytic reduction efficient.React 3h under the condition that does not add any reducing substances, the average degradation rate of PFOA can reach 43%; And under the air atmosphere condition, the average degradation rate of PFOA only has 29%.This sufficient reacting has proved that PFOA is that approach by photo catalytic reduction is degraded.
The photocatalytic degradation of embodiment 2, perfluoro octyl sulfonic acid salt (PFOS)
To 100mL 7.25 * 10 -5Add β-Ga in the PFOS aqueous solution of mol/L 2O 3Powder and reducing substances Na 2S 2O 3, stir 3h, the homogeneous phase solution that obtains clarifying, β-Ga in the homogeneous phase solution 2O 3Final concentration be 2.67 * 10 -3Mol/L, Na 2S 2O 3Concentration be 5 * 10 -5Mol/L.
As shown in Figure 1, open the aeration board 4 of reaction unit bottom, nitrogen is added inlet 5 from gas be passed into the reaction vessel 3, homogeneous phase solution with the above-mentioned clarification that obtains joins in the reactor 3 again, aeration is opened cooling water circulating device 7 and light source 1 about half an hour then, begins reaction.Extract reaction solution from sample tap 8 at regular intervals, detect PFOS and short chain perfluorocarboxylic acid compound concentrations thereof, adopt electron spray anion (ESI) pattern among the UPLC-MS/MS to measure PFOS and short chain perfluorocarboxylic acid compound concentrations thereof.
Three repetitions, β-Ga are established in experiment 2O 3The effect of photocatalytic degradation PFOS as shown in Figure 3.The result shows that under nitrogen atmosphere, PFOS can be effectively by photocatalytic degradation, reaction 3h, and the average degradation rate of PFOS can reach 81%.
The photocatalytic degradation of PFOA under embodiment 3, the reducing substances existence condition
To 100mL 7.25 * 10 -5Add β-Ga in the PFOA aqueous solution of mol/L 2O 3Powder, and then in above-mentioned solution, add reducing substances KI, Na respectively 2S 2O 3And methyl alcohol, stir 3h, the homogeneous phase solution that obtains clarifying, β-Ga in the homogeneous phase solution 2O 3Final concentration be 2.67 * 10 -3Mol/L, KI, Na 2S 2O 3Be respectively 5 * 10 with the final concentration of methyl alcohol -5Mol/L.
As shown in Figure 1, open the aeration board 4 of reaction unit bottom, nitrogen is added inlet 5 from gas be passed into the reaction vessel 3, homogeneous phase solution with the above-mentioned clarification that obtains joins in the reactor 3 again, aeration is opened cooling water circulating device 7 and light source 1 about half an hour then, begins reaction.Extract reaction solution from sample tap 8 at regular intervals, detect PFOA and short chain perfluorocarboxylic acid compound concentrations thereof, adopt electron spray anion (ESI) pattern among the UPLC-MS/MS to measure PFOA and short chain perfluorocarboxylic acid compound concentrations thereof.
Three repetitions, β-Ga under the reducing substances existence condition are established in experiment 2O 3The effect of photocatalytic degradation PFOA as shown in Figure 4.The result shows, the adding of reducing substances has promoted the efficient of photocatalytic degradation PFOA greatly, its reason is the reducing substances oxidation material (mainly being light induced electron and dissolved oxygen) in the catching reaction system effectively, thereby improved the concentration of light induced electron, promoted photo catalytic reduction efficient.Reaction 3h adds reducing substances Na 2S 2O 3System on average improved 55% than the photocatalytic degradation efficient of the system that does not add reducing substances.
The photo catalytic reduction defluorinate of embodiment 4, PFOA
To 100mL 7.25 * 10 -5Add β-Ga in the PFOA aqueous solution of mol/L 2O 3Powder and reducing substances Na 2S 2O 3, stir 3h, the homogeneous phase solution that obtains clarifying, β-Ga in the homogeneous phase solution 2O 3Final concentration be 2.67 * 10 -3Mol/L, Na 2S 2O 3Concentration be 5 * 10 -5Mol/L.
As shown in Figure 1, open the aeration board 4 of reaction unit bottom, nitrogen is added inlet 5 from gas be passed into the reaction vessel 3, homogeneous phase solution with the above-mentioned clarification that obtains joins in the reactor 3 again, aeration is opened cooling water circulating device 7 and light source 1 about half an hour then, begins reaction.Extract reaction solution from sample tap 8 at regular intervals, adopt the concentration of fluorine ion in the chromatography of ions detection reaction liquid, can calculate the defluorinate efficient of PFOA according to the variation of fluorinion concentration in the reactant liquor.
Three repetitions are established in experiment, and the effect of photocatalysis defluorinate as shown in Figure 5.The result shows, reducing substances Na 2S 2O 3Adding promoted the efficient of photocatalysis defluorinate greatly.Reaction 3h, the defluorinate rate of PFOA reaches 31%, promptly on average has 4.6 fluorine atoms to split away off from the PFOA molecule; And do not add reducing substances Na 2S 2O 3Reaction system, have only 14% defluorinate rate.
The intermediate product of embodiment 5, photocatalytic degradation PFOA and change in concentration thereof
To 100mL 7.25 * 10 -5Add β-Ga in the PFOA aqueous solution of mol/L 2O 3Powder and reducing substances Na 2S 2O 3 2, stir 3h, the homogeneous phase solution that obtains clarifying, β-Ga in the homogeneous phase solution 2O 3Final concentration be 2.67 * 10 -3Mol, Na 2S 2O 3Concentration be 5 * 10 -5Mol/L.
As shown in Figure 1, open the aeration board 4 of reaction unit bottom, nitrogen is added inlet 5 from gas be passed into the reaction vessel 3, homogeneous phase solution with the above-mentioned clarification that obtains joins in the reactor 3 again, aeration is opened cooling water circulating device 7 and light source 1 about half an hour then, begins reaction.Extract reaction solution from sample tap 8 at regular intervals, adopt UPLC-MS/MS to measure PFOA and short chain perfluorocarboxylic acid compound concentrations thereof.
Three repetitions are established in experiment, and PFOA and short chain perfluorocarboxylic acid compound concentrations measurement result thereof are as shown in Figure 6.The result shows, reaction 3h, and PFOA is almost degraded fully, and has produced the C of a series of short chains nH 2n+1COOH (1＜n＜7).If the reaction time long enough, the C of short chain nH 2n+1COOH also can be decomposed gradually.

Claims (10)

1, a kind of method for degrading perfluorinated compounds may further comprise the steps: under oxygen free condition, adopt β-Ga 2O 3As photochemical catalyst, be the UV-irradiation fluorine substituted compounds of 185-254nm with wavelength, make the fluorine substituted compounds degraded.
2, method according to claim 1 is characterized in that: described fluorine substituted compounds is perfluoro caprylic acid or perfluoro octyl sulfonic acid salt.
3, method according to claim 1 and 2 is characterized in that: described oxygen free condition is by feeding inert gas or reducibility gas realization in reaction system.
4, according to arbitrary described method among the claim 1-3, it is characterized in that: described ultraviolet light wavelength is 254nm.
5, according to arbitrary described method among the claim 1-4, it is characterized in that: described fluorine substituted compounds and β-Ga 2O 3Mol ratio be 1: (15-40).
6, method according to claim 5 is characterized in that: described fluorine substituted compounds and β-Ga 2O 3Mol ratio be 1: 37.
7, according to arbitrary described method among the claim 1-6, it is characterized in that: described method also comprises the step that adds reducing substances in reaction system;
Described reducing substances is solubility salt compounded of iodine, solubility thiosulfate or organic matter.
8, method according to claim 7 is characterized in that: described solubility salt compounded of iodine is a KI, and described solubility thiosulfate is a sodium thiosulfate, and described organic matter is methyl alcohol or phenol.
9, according to arbitrary described method among the claim 1-8, it is characterized in that: the mol ratio of described fluorine substituted compounds and described reducing substances is 1: (0-15), be preferably 1: 0.7.
10, the application of arbitrary described method in the fluorine substituted compounds degraded among the claim 1-9.
CN200910081468A 2009-04-08 2009-04-08 Method for degrading perfluorinated compounds Pending CN101524583A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102276012A (en) * 2011-07-27 2011-12-14 北京师范大学 Method for purifying perfluorooctane sulfonate in water by photocatalysis in simulated sunlight
CN103936096A (en) * 2014-04-21 2014-07-23 青岛理工大学 Method for degrading perfluorocarboxylic acid pollutant by utilizing microwave radiation
CN105060389A (en) * 2015-07-16 2015-11-18 广西大学 Method for photocatalytic degradation of PFOA (perfluorooctanoic acid) in water through noble-metal-doped gallium oxide
CN106082389A (en) * 2016-08-11 2016-11-09 上海大学 Utilize perfluoro caprylic acid or the method for Perfluorooctane sulfonates in irradiation-induced degradation water body
CN108276245A (en) * 2018-01-08 2018-07-13 中国科学院化学研究所 A method of utilizing photo catalytic reduction perfluoro aromatic compound to part fluoro aromatic compound
CN108828128A (en) * 2018-06-20 2018-11-16 清华大学 A method of total Organic fluoride in measurement water sample and aqueous solution
CN109554679A (en) * 2019-01-21 2019-04-02 北京工业大学 It is a kind of to utilize Nb doping enhancing Ga2O3The method of film photocatalysis degradation organic contaminant
CN114276600A (en) * 2021-12-23 2022-04-05 南通宝加利新材料有限公司 Preparation method of degradable PE film

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102276012A (en) * 2011-07-27 2011-12-14 北京师范大学 Method for purifying perfluorooctane sulfonate in water by photocatalysis in simulated sunlight
CN102276012B (en) * 2011-07-27 2012-10-31 北京师范大学 Method for purifying perfluorooctane sulfonate in water by photocatalysis in simulated sunlight
CN103936096A (en) * 2014-04-21 2014-07-23 青岛理工大学 Method for degrading perfluorocarboxylic acid pollutant by utilizing microwave radiation
CN103936096B (en) * 2014-04-21 2015-05-13 青岛理工大学 Method for degrading perfluorocarboxylic acid pollutant by utilizing microwave radiation
CN105060389A (en) * 2015-07-16 2015-11-18 广西大学 Method for photocatalytic degradation of PFOA (perfluorooctanoic acid) in water through noble-metal-doped gallium oxide
CN106082389A (en) * 2016-08-11 2016-11-09 上海大学 Utilize perfluoro caprylic acid or the method for Perfluorooctane sulfonates in irradiation-induced degradation water body
CN108276245A (en) * 2018-01-08 2018-07-13 中国科学院化学研究所 A method of utilizing photo catalytic reduction perfluoro aromatic compound to part fluoro aromatic compound
CN108828128A (en) * 2018-06-20 2018-11-16 清华大学 A method of total Organic fluoride in measurement water sample and aqueous solution
CN108828128B (en) * 2018-06-20 2019-08-13 清华大学 A method of total Organic fluoride in measurement water sample and aqueous solution
CN109554679A (en) * 2019-01-21 2019-04-02 北京工业大学 It is a kind of to utilize Nb doping enhancing Ga2O3The method of film photocatalysis degradation organic contaminant
CN114276600A (en) * 2021-12-23 2022-04-05 南通宝加利新材料有限公司 Preparation method of degradable PE film

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